US5376736A - Transparent polycarbonate PET blends - Google Patents

Transparent polycarbonate PET blends Download PDF

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Publication number
US5376736A
US5376736A US08/226,901 US22690194A US5376736A US 5376736 A US5376736 A US 5376736A US 22690194 A US22690194 A US 22690194A US 5376736 A US5376736 A US 5376736A
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aromatic polycarbonate
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composition
carbon atoms
group
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US08/226,901
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English (en)
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James P. Mason
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Bayer Corp
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Miles Inc
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Assigned to MILES INC. reassignment MILES INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MASON, JAMES P.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the invention relates to thermoplastic molding compositions and more particularly to compositions containing polyethylene terephthalate.
  • Thermoplastic molding compositions are disclosed containing (i) about 1 to 89% polyethylene terephthalate (ii) about 10 to 89% of a first aromatic polycarbonate (PC1) and (iii) about 1-89% of the second aromatic polycarbonate (PC2).
  • PC1 is a copolycarbonate which contains about 5 to 70 mole percent of structural units derived from a dihydroxy compound the bridging unit of which corresponds to ##STR2## wherein R 3 , R 4 , X and m are defined.
  • a composition of the invention is characterized in a TLT value which is an improvement over that of the corresponding composition which contains the same amount of PET and only PC1.
  • An additional embodiment of the invention concerns a method for increasing the TLT of a thermoplastic molding composition containing PET and PC1. The method comprises replacing some of said PC1 by PC2.
  • Thermoplastic molding compositions are being used in a wide variety of applications because of their attractive profile of mechanical and physical properties.
  • a key property for many applications is the transparency of the composition.
  • Blends of polycarbonates (PC1) and polyethylene terephthalate (PET) are known and have been used in applications where enhanced chemical resistance is desired. It has been the experience of workers in the art that the TLT values of blends of PET and polycarbonate are lower than those of the individual components.
  • a commercial product containing terephthalates of ethylene glycol and cyclohexane dimethanol and polycarbonate is noted for its transparency.
  • the relevant art is noted to include U.S. Pat. No.
  • thermoplastic compositions containing PET and (co)polycarbonate having improved TLT It is a further object of the invention to provide thermoplastic compositions containing PET and (co)polycarbonate having improved TLT.
  • the inventive thermoplastic molding compositions contains
  • a composition of the invention is characterized in a TLT value which is an improvement over that of the corresponding composition which contains the same amount of PET and only PC1.
  • the compositions of the invention have TLT value greater than 80%.
  • the first aromatic polycarbonate resin is derived from dihydroxy compounds having no special cyclic bridging units (herein sometimes referred to as PC1) and the second aromatic polycarbonate resin is a copolycarbonate which contains at least some structural units derived from a dihydroxy compound having special cyclic bridging units (herein sometimes referred to as PC2).
  • PC1 dihydroxy compounds having no special cyclic bridging units
  • PC2 copolycarbonate which contains at least some structural units derived from a dihydroxy compound having special cyclic bridging units
  • the second aromatic polycarbonate resin (PC2) is a copolycarbonate which contains about 5 to 70 mole percent, preferably 10 to 55 mole percent of structural units derived from at least one dihydroxy compound which contains special cyclic bridging units, the remaining structural units are derived from any of the dihydroxy compounds noted earlier as the source for PC1.
  • the special bridging unit corresponds to ##STR3## wherein R 3 and R 4 independently one of the other represent a hydrogen atom or a C 1-6 alkyl and X denotes carbon, with the proviso that R 3 and R 4 both represent an alkyl radical on at least one of the X carbon atoms, and where m is an integer of 4 to 10.
  • the invention thus also relates to a method for increasing the TLT values of a thermoplastic molding composition which contains polyethylene terephthalate and said first polycarbonate resin. Increasing the TLT was found to result upon replacing some of said first aromatic polycarbonate resin by PC2.
  • the TLT value of the composition being determined in accordance with ASTM D-1003 using specimens 0.100" in thickness.
  • the polyethylene terephthalate useful in the present context is a well know thermoplastic resin which is readily available in commerce. It is derived from terephthalic acid and ethylene diol and is characterized in that its intrinsic viscosity is at least 0.4, preferably 0.4 to 1.4, most preferably 0.4 to 1.1 deciliter per gram, as measured in a 1 percent solution of phenol and tetrachloroethane (60:40) at 25° C.
  • the aromatic terephthalic acid component may be combined with up to 15 percent of additional acid component, including at least one of isophthalic acid, naphthalene-dicarboxylic acid, diphenylether dicarboxylic acid, diphenyldicarboxylic acid, diphenylsulphone dicarboxylic acid, and diphenoxyethane dicarboxylic acid.
  • additional acid component including at least one of isophthalic acid, naphthalene-dicarboxylic acid, diphenylether dicarboxylic acid, diphenyldicarboxylic acid, diphenylsulphone dicarboxylic acid, and diphenoxyethane dicarboxylic acid.
  • hydroxycarboxylic acids which are not aromatic, including aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid.
  • the diol component may contain in addition to ethylene glycol up to 15 percent relative to the molar amount of the glycol of co-diols.
  • These include aliphatic diols having 3 to 8 carbon atoms, cycloaliphatic diols having 6 to 15 carbon atoms or aromatic diols having 6 to 21 carbon atoms.
  • co-diols examples include 3-methylpentane diol(2,4), 2-methyl-pentadiol-(1,4), 2,2,4-trimethylpentanediol-(1,3), 2-ethylhexanediol (1,3), 2,2-diethylpropanediol-(1,3), hexane diol(1,3), 1,4-di(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-hydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3-hydroxyethoxyphenylpropane, and 2,2-bis(4-hydroxypropoxyphenyl)-propane.
  • the polyesters may be branched by incorporating trihydric or tetrahydric alcohols or tribasic or tetrabasic acids of the type and in the manner known in the art. Chain terminators suitable in the preparation of such polyesters are also well known in the art.
  • polyester resin for the preparation of suitable polyester resin are known and have been described in U.S. Pat. Nos. 2,463,319 and 3,047,539 which are incorporated herein by reference. Most suitable in the present context is polyethylene terephthalate.
  • the first polycarbonate resin is derived from at least one dihydroxy compound conforming to formula (1) or (2) ##STR4## wherein A denotes an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a carbonyl group, an oxygen atom, --S--, --SO-- or --SO 2 -- radical or a radical conforming to ##STR5## and wherein g denotes 0 or 1, e denotes 0 or 1, d denotes 0 to 4 and f denotes 0 to 3, and where the several Z substituents independently one of the other denotes F, Cl, Br or an alkyl group having 1 to 4 carbon atoms with the proviso that dihydroxydiphenyl cyclohexane conforming to formula (3) are excluded.
  • A denotes an alkylene group
  • dihydroxy compounds in the practice of the invention are hydroquinone, resorcinol, bis-(hydroxypheny) alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)sulfoxides. bis-(hydroxyphenyl)sulfones and 2,2-bis(hydroxyphenyl)-diisopropyl-benzenes.
  • aromatic dihydroxy compounds are described. for example in U.S. Pat. Nos.
  • suitable bisphenols are 2,2-bis-(4-hydroxy-phenyl)-propane-(bisphenol A), 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(4-hydroxyphenyl)-p-diisopropyl-benzene, 2,2-bis(3-chloro-4-hydroxyphenyl)-propane, hydroxybenzophenone and 4,4'-sulfonyl diphenol.
  • bisphenol A 2,2-bis-(4-hydroxyphenyl)propane
  • the polycarbonates of the invention may entail in their structure, units derived from one or more of the suitable bisphenols.
  • polycarbonate resins may be carried out in accordance with any of the processes Known in the art, for example, by the interfacial polycondensation process in a homogeneous phase or by transesterification.
  • monofunctional reactants such as monophenols may be used in order to limit their respective molecular weights.
  • branching agents may be employed. Branching may be obtained by the incorporation of small amounts, preferably of between about 0.05 and 2.0 mol percent (relative to diphenols employed), of trifunctional or more than trifunctional compounds, especially compounds having three or more phenolic hydroxyl groups.
  • Polycarbonates of this type are described, for example, in German Offenlegungsschriften (German Published Specifications) Nos. 1,570,533; 1,595,762; 2,116,974 and 2,113,347, British Specification No. 1,079,821 and U.S. Pat. No. 3,544,514 (incorporated herein by reference).
  • Some examples of compounds with three or more than three phenolic hydroxyl groups which can be used are phloroglucinol, 4,6-dimenthyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 2,4,6-trimethyl-2,4,6,tri-(4-hydroxyphenyl)-heptane, 1,4,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxy-phenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, 6-bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, hexa(4-(4-hydroxyphenyliso
  • trifunctional compounds are 2,4-dihydroxy-benzoic acid, trimesic acid, dyanuric chloride and 3,3-bis-(4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
  • phenolphthalene based polycarbonate phenolphthalene based polycarbonate
  • copolycarbonates terpolycarbonates
  • terpolycarbonates such as are described in U.S. Pat. Nos. 3,036,036 and 4,210,741, both incorporated by reference therein.
  • the second aromatic polycarbonate resin contains about 5 to 70 mole percent, preferably 10 to 55 mole percent of structural units derived from at least one dihydroxy compound which contains said special cyclic bridging units, the remaining structural units are derived from any of the dihydroxy compounds noted earlier as the source for PC1.
  • R 1 and R 2 independently represent hydrogen, halogen, preferably chlorine or bromine, C 1-8 alkyl, C 5-6 cycloalkyl, C 6-10 aryl, preferably phenyl, and C 7-2 aralkyl, preferably phenyl-C 1-4 alkyl, in particular benzyl;
  • m denotes an integer of 4 to 10, preferably 4-7;
  • R 3 and R 4 independently one of the other represent a hydrogen atom or a C 1-6 alkyl and X denotes carbon, with the proviso that R 3 and R 4 both represent an alkyl radical on at least one of the X carbon atoms.
  • both R 3 and R 4 represent alkyl on one or 2 ⁇ carbon atoms, most preferably only on one X carbon atom.
  • Methyl is the preferred alkyl radical; the X atoms in the alpha position to the diphenyl substituted carbon atom (C-1) are preferably not dialkyl substituted; two alkyl substituents in the beta-position to C-1 is preferred.
  • the comonomers entailed in the preparation of the second aromatic polycarbonate of the invention may be any of the dihydroxy compound mentioned earlier in connection with PC1.
  • the preparation of PC2 follows the same methods and the same monofunctional reactants and optional branching agents as mentioned earlier in connection with the preparation of PC1.
  • compositions in accordance with the invention have been prepared and their properties evaluated.
  • the preparation of the compositions in a twin screw extruder followed conventional procedures, Test specimens measuring 0.100" (thickness) were molded by injection following conventional procedures, TLT values were determined following the procedure described in ASTM D-1003 using a Match-Scan I Spectrophotometer (Diano Corporation).
  • the following materials were used in preparing the compositions described below: PET: a polyethyleneterephthalate having an intrinsic viscosity of about 1.0; a product of Eastman; Polycarbonate (PC1): a homopolycarbonate based on bisphenol-A, having a melt flow rate of 6.5; a product of Miles Inc.
  • PC2 polycarbonate resin

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lock And Its Accessories (AREA)
  • Polyesters Or Polycarbonates (AREA)
US08/226,901 1993-02-08 1994-04-12 Transparent polycarbonate PET blends Expired - Lifetime US5376736A (en)

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US08/226,901 US5376736A (en) 1993-02-08 1994-04-12 Transparent polycarbonate PET blends

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US1490193A 1993-02-08 1993-02-08
US9383493A 1993-07-19 1993-07-19
US08/226,901 US5376736A (en) 1993-02-08 1994-04-12 Transparent polycarbonate PET blends

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0683208A3 (fr) * 1994-05-18 1999-01-20 Bayer Corporation Matières transparentes de polycarbonates
US20060194910A1 (en) * 2004-05-19 2006-08-31 Nobuo Miyatake Stabilization of polymers with zinc oxide nanoparticles
US20090029167A1 (en) * 2007-07-24 2009-01-29 The Texas A&M University System Polymer nanocomposites including dispersed nanoparticles and inorganic nanoplatelets
EP2333011A1 (fr) * 2009-12-12 2011-06-15 Bayer MaterialScience AG Compositions de polycarbonate dotées d'une dureté de surface améliorée

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5104723A (en) * 1988-10-06 1992-04-14 Bayer Aktiengesellschaft Mixtures of special new polycarbonates with other thermoplastics or with elastomers
US5132154A (en) * 1989-06-06 1992-07-21 Bayer Aktiengesellschaft Polycarbonate mixtures in optical applications

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5104723A (en) * 1988-10-06 1992-04-14 Bayer Aktiengesellschaft Mixtures of special new polycarbonates with other thermoplastics or with elastomers
US5132154A (en) * 1989-06-06 1992-07-21 Bayer Aktiengesellschaft Polycarbonate mixtures in optical applications

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0683208A3 (fr) * 1994-05-18 1999-01-20 Bayer Corporation Matières transparentes de polycarbonates
US20060194910A1 (en) * 2004-05-19 2006-08-31 Nobuo Miyatake Stabilization of polymers with zinc oxide nanoparticles
US20090029167A1 (en) * 2007-07-24 2009-01-29 The Texas A&M University System Polymer nanocomposites including dispersed nanoparticles and inorganic nanoplatelets
US8344054B2 (en) * 2007-07-24 2013-01-01 The Texas A & M University System Polymer nanocomposites including dispersed nanoparticles and inorganic nanoplatelets
EP2333011A1 (fr) * 2009-12-12 2011-06-15 Bayer MaterialScience AG Compositions de polycarbonate dotées d'une dureté de surface améliorée
EP2336245A1 (fr) * 2009-12-12 2011-06-22 Bayer MaterialScience AG Compositions de polycarbonate dotées d'une dureté de surface améliorée

Also Published As

Publication number Publication date
MX9400935A (es) 1994-08-31
CA2113501A1 (fr) 1994-08-09
CA2113501C (fr) 2007-09-18

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